WO2005087873A2 - Composes cer comme promoteurs de durcissement par rayonnement - Google Patents

Composes cer comme promoteurs de durcissement par rayonnement Download PDF

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WO2005087873A2
WO2005087873A2 PCT/EP2005/002731 EP2005002731W WO2005087873A2 WO 2005087873 A2 WO2005087873 A2 WO 2005087873A2 EP 2005002731 W EP2005002731 W EP 2005002731W WO 2005087873 A2 WO2005087873 A2 WO 2005087873A2
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Prior art keywords
cerium
meth
compounds
acid
vinyl
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PCT/EP2005/002731
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German (de)
English (en)
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WO2005087873A3 (fr
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Nick Gruber
Reinhold Schwalm
Erich Beck
Yvonne Heischkel
Christian Decker
Katia Studer
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Basf Aktiengesellschaft
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths

Definitions

  • the present invention relates to the use of cerium compounds as initiators for radiation curing and coating compositions which contain cerium compounds.
  • cerium salts and polymerization inhibitors are known systems for stabilizing ethylenically unsaturated compounds against undesired polymerization, for example from US Pat. No. 4,542,231.
  • No. 3,755,234 describes the graft or block polymerization of polyvinyl alcohols in the presence of tetravalent cerium compounds.
  • the polymerization is thermally induced and takes place at elevated temperatures of 40 - 65 ° C.
  • Acidic, aqueous solutions are disclosed as solvents for the cerium compounds; the aim is to carry out the polymerization at a pH below 6.0, preferably below 3.0. Light-induced polymerization is not disclosed.
  • WO 94/24207 describes the graft polymerization of ethylenically unsaturated compounds onto active hydrogen-containing compounds using peroxides as radical polymerization catalysts which are activated by metal ions, such as Ce + or Ce 3+ .
  • peroxides as radical polymerization catalysts which are activated by metal ions, such as Ce + or Ce 3+ .
  • metal ions such as Ce + or Ce 3+ .
  • a combination of peroxide and heavy metal ions, including cerium salts, for starting graft polymerization is also disclosed in DE-A1 19806745.
  • cerium compound does not function as a polymerization initiator but as an activator for the actual catalyst, the peroxide.
  • Banerjee et al. therefore do not recognize the suitability of cerium compounds for the polymerization.
  • the object of the present invention was to provide radiation-curable coating compositions in which cerium compounds are used as free radical initiators and which have properties which are improved compared to the prior art.
  • the coating composition is preferably used for statistical, radical (co) polymerization.
  • Cerium (IV) compounds for the purposes of this invention are those compounds which contain at least one Ce 4+ cation with any counterions.
  • Possible counterions are F “ , CI “ , CIO “ , CIO 3 ⁇ , CIO 4 “ , Br ⁇ J “ , JO 3 “ , CN “ , OCN “ SCN “ , NO 2 -, NO 3 -, HCO 3 “ , COg 2 " , S ⁇ , SH “ , HSO 3 _ , SO 3 2 -, HSO 4 " , SO 4 2” , S 2 O 2 2 -, S 2 O 4 2_ , S 2 O 5 2 -, S 2 O 6 2 -, S 2 O 7 2 -, S 2 O 8 2 ⁇ H 2 PO 2 ⁇ H 2 PO 4 " HPO PO PaO dithiocarbamate, salicylate, (OC p H 2p + 1 ) ⁇ , (C p H 2p _ ⁇ O 2 ) -, (C p H 2 p_ 3 O 2 and (C p + 1 H 2 p_ 2 O 4 ) 2 " , where p stands
  • Carboxylates may also be mentioned, in particular formate, acetate, propionate, hexanoate and 2-ethylhexanoate and oxalate, acetylacetonate, acrylate and methacrylate, preferably formate, acetate, propionate, oxalate, acetylacetonate, acrylate and methacrylate.
  • These salts can also be present as hydrates, which are equally suitable.
  • Preferred cerium (IV) compounds are ammonium hexanitrate cerate (IV) (cerium (IV) ammonium nitrate, (NH 4 ) 2 [Ce (NO 3 ) 6 ⁇ ), sodium hexanitrate cerate (IV) (Na 2 [Ce (NO 3 ) 6 ]) , Potassium hexanitrate cerate (IV) (K 2 [Ce (NO 3 ) 6 ]), cerium (IV) ammonium sulfate (Ce (NH 4 ) 2 (NO 3 ) 6 )), cerium (IV) hydroxide, cerium (IV) isopropylate Isopropanol complex, cerium (IV) oxide (CeO 2 ) and cerium (IV) sulfate (Ce (SO 4 ) 2 ).
  • cerium compounds with an oxidation state lower than +4 and to convert them into a cerium (IV) compound in the coating composition with the aid of an oxidizing agent, in particular cerium (III) compounds.
  • cerium (III) compounds are cerium (III) acetate, cerium (III) hydrate, cerium (III) acetylacetonate, cerium (III) acetylacetonate hydrate, cerium (III) bromide, cerium (III) carbonate, cerium (III) ) carbonate hydrate, cerium (III) chloride (CeCI 3 ), cerium (III) chloride heptahydrate, cerium (III) ethylhexanoate and its solutions or dispersions in mineral oil or naphtha (Octa Soliogen Cerium® 6 and 10 from Borcherts, Monheim, Germany, CAS number [58797-01-4]), cerium (III) fluoride, cerium (III) nitrate (Ce (NO 3 ) 3 ) .
  • suitable oxidizing agents are those which in turn do not trigger any polymerization, i.e. are not radical formers.
  • cerium compounds as cerium (IV) compounds.
  • the cerium compounds can also be used as complexes, for example complexed with ligands containing amine, sulfur, nitrogen, phosphorus and / or oxygen, or as cyclopentadienyl complexes.
  • ligands are mercaptans, sulfides, primary, secondary or tertiary amines, primary, secondary or tertiary phosphines, alcohols and ethers as well as cyclopentadiene, benzene, furan, pyrrole, pyridine and thiophene, and also their derivatives, and also complexing agents such as ethanolamines, ethylenediaminetetraacetate , Ethylenediamine triacetate, nitrilotriacetic acid and the like.
  • the purity of the cerium salts used is not essential according to the invention; in general it is sufficient if the salt is in technical purity, for example 80% or more, preferably at least 90%, particularly preferably at least 95%, very particularly preferably at least 98 % and in particular at least 99%.
  • the salts can also be used in higher or lower purities. Mixtures of several cerium salts can of course also be used, for example of two or three cerium salts, but the use of a cerium salt is preferred.
  • the cerium compound is generally present in amounts of up to 2% by weight (based on the total coating composition), preferably up to 1.5, particularly preferably up to 1.0, very particularly preferably up to 0.5%. -%.
  • the cerium compound is usually contained in amounts of at least 0.01% by weight, preferably at least 0.05, particularly preferably at least 0.1 and very particularly preferably at least 0.2% by weight.
  • the cerium compounds can be used in a mixture with other photoinitiators.
  • photoinitiators known to the person skilled in the art, e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K.K. Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymeri ⁇ ation, P.K.T. Oldring (Eds), SITA Technology Ltd, London.
  • at least one further photoinitiator is present in addition to the cerium compound.
  • mono- or bisacylphosphine oxides are suitable, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ® TPO from BASF AG), ethyl 2,4,6-trimethylbenzoylphenylphosphinate (Lucirin ® TPO L from BASF AG), bis (2,4,6-trimethylbenzoyl) phenyiphosphine oxide (Irgacure® 819 from Ciba Specialty Chemicals) , Benzophenone, hydroxyacetophenone, phenylglyoxylic acid and their derivatives or mixtures of these photoinitiators.
  • 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ® TPO from BASF AG)
  • ethyl 2,4,6-trimethylbenzoylphenylphosphinate (Lucirin ® TPO L from BASF AG)
  • Examples include benzophenone, acetophenone, acetone naphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberon, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diachenylbenzene, p-diacetylbenzene, p-diacetylbenzene, p-diacetylbenzene, p-diacetylbenzene, p-diacetylbenzene, p-diacetylbenzene, p-diacetyl-benzo-4-diacetyl-benzo-4-diacetyl-benzophenone -Methoxyacetophenone, ß-methylanthraquinone, terf-buty
  • Non-yellowing or little yellowing photoinitiators of the phenylglyoxalic acid ester type are also suitable, as described in DE-A 19826712, DE-A 199 13353 or WO 98/33761.
  • photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, benzophenone, 1-benzoylcyclohexan-1-ol , 2-hydroxy-2,2-dimethyl-acetophenone and 2,2-dimethoxy-2-phenylacetophenone.
  • At least one solvent can be used in the coating compositions according to the invention.
  • Suitable solvents are those in which the cerium compound in question is soluble and which does not lead to any undesirable reactions with the monomer.
  • Such solvents are, for example, water, (meth) acrylic acid (ester), acetone, acetylacetone, acetoacetic ester, lower alcohols, such as e.g. Methanol, ethanol, / so-propanol, n-propanol, n-butanol, / so-butanol, se c-butanol, fe / f-butanol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Ethylene glycol di-n-butyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, polyethylene glycols with a molecular weight of up to 898, polypropylene glycols with a molecular weight of 134 to 308, lower carboxylic acids, such
  • Preferred solvents are those in which the cerium compound is soluble to at least 0.5, preferably at least 1, particularly preferably at least 2, very particularly preferably at least 5 and in particular at least 10% by weight and which in turn is in the quantitative ratio used with the coating composition are miscible.
  • Water, methanol, ethanol, / so-propanol, n-propanol, n-butanol, ethylene glycol, diethylene glycol, ethylene glycol dimethyl ether, THF, dioxane, acetonitrile, propionitrile, dimethylformamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, 1 are very particularly preferred , 2-ethylene carbonate and 1, 2-propylene carbonate.
  • Water, methanol, ethanol, / so-propanol, n-propanol, n-butanol, ethylene glycol, THF, dioxane, acetonitrile, dimethylformamide and dimethyl sulfoxide are particularly preferred.
  • water or an aqueous medium is used as the solvent, it is advantageous that it is neither too acidic nor too alkaline, since this can impair the paint properties. It is therefore preferred that water or an aqueous medium used as a solvent has a pH between 3 and 11, particularly preferably between 4 and 10, very particularly preferably between 5 and 9 and in particular between 6 and 8.
  • Radically polymerizable compounds in the coating compositions according to the invention are those compounds which have at least one, for example 1 to 6, preferably 1 to 4 and particularly preferably 1 to 3 groups which are capable of free radical polymerization.
  • Radically polymerizable groups are, for example, vinyl ether or (meth) acrylate groups, preferably (meth) acrylate groups and particularly preferably acrylate groups.
  • Monofunctional, polymerizable compounds are those with exactly one radical-polymerizable group
  • multifunctional, polymerizable compounds are those with more than one, preferably with at least two, radical-polymerizable groups.
  • Monofunctional, polymerizable compounds are, for example, esters of (meth) acrylic acid with alcohols which have 1 to 20 carbon atoms, for example methyl (meth) acrylic acid, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid-2 ethylhexyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dihydrodicyclopentadienyl acrylate, vinyl aromatic compounds, for example styrene, divinylbenzene, ⁇ , ⁇ -unsaturated nitriles, for example acrylonitrile, methacrylonitrile , ⁇ , ⁇ -unsaturated aldehydes, for example acrolein, methacrolein, vinyl esters, for example vinyl acetate, vinyl propionate, halogenated eth
  • N-vinyl acetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide or vinyl ether for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, / so-propyl vinyl ether, n-butyl vinyl ether, se / butyl vinyl ether, / so-butyl vinyl ether, terf-butyl vinyl ether, 4-hydroxybutyl vinyl ether, and mixtures thereof.
  • esters of (meth) acrylic acid particularly preferred are (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester and 2-hydroxyethyl acrylate, all (Meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester and 2-hydroxyethyl acrylate and in particular 2-hydroxyethyl acrylate are particularly preferred.
  • (meth) acrylic acid stands for methacrylic acid and acrylic acid, preferably for acrylic acid.
  • Multifunctional, polymerizable compounds are preferably multifunctional (meth) acrylates which carry more than 1, preferably 2-10, particularly preferably 2-6, very particularly preferably 2-4 and in particular 2-3 (meth) acrylate groups, preferably acrylate groups.
  • esters of (meth) acrylic acid with correspondingly at least dihydric polyalcohols can be, for example, esters of (meth) acrylic acid with correspondingly at least dihydric polyalcohols.
  • Such polyalcohols are, for example, at least divalent polyols, polyether or polyesterols or polyacrylate polyols with an average OH functionality of at least 2, preferably 3 to 10, suitable.
  • multifunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate Octanediol diacrylate, neopentyl glycol diacrylate, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol diacrylate, 1,2-, 1,3- or 1,4-cyclohexanediol diacrylate, trimethylolpropane triacrylate, di- trimethylolpropane penta- or hexaacrylate, pentaerythritol tri- or tetraacrylate, glyceryl or triacrylate, as well as di- and polyacrylates of sugar alcohols, such as
  • R 1 and R 2 independently of one another are hydrogen or C 1 -C 18 -alkyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
  • k, I, m, q each independently represent an integer from 1 to 10, preferably 1 to 5 and particularly preferably 1 to 3 and
  • d • - C 18 alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles means, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl , preferably methyl, ethyl or n-propyl, very particularly preferably methyl or ethyl.
  • Preferred multifunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyether polyol acrylate and polyether polyol acrylate, polyether polyol acrylate and polyether polyol acrylate alkoxylated, particularly preferably ethoxylated trimethylolpropane.
  • Very particularly preferred multifunctional, polymerizable compounds are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and triacrylate of trimethylolpropane ethoxylated once to twenty times.
  • Polyester polyols are e.g. from Ulimann's Encyklopadie der Technische Chemie, 4th edition, volume 19, pp. 62 to 65. Polyester polyols are preferably used which are obtained by reacting dihydric alcohols with dihydric carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures can also be used to prepare the polyester polyols.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include:
  • Dicarboxylic acids of the general formula HOOC- (CH 2 ) y -COOH are preferred, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • polyesterols into consideration 1,2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, poly-THF with a molecular weight between 162 and 2000, poly -1,3-propanediol with a molecular weight between 134 and 1178, poly-1,2-propanediol with a molecular weight between 134 and 898, polyethylene glycol with a molecular weight between 106 and 458, neopentyl glycol, hydroxyp
  • Alcohols of the general formula HO- (CH 2 ) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • Ethylene glycol, butane-1,4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1,12-diol are preferred.
  • Neopentyl glycol is also preferred.
  • polycarbonate diols such as those e.g. can be obtained by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyester polyols.
  • Lactone-based polyester diols are also suitable, these being homopolymers or copolymers of lactones, preferably addition products of lactones with terminal hydroxyl groups onto suitable difunctional starter molecules.
  • Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit also by a C to C alkyl radical can be substituted. Examples are ⁇ -caprolactone, ß-propiolactone, gamma-butyrolactone and / or methyl- ⁇ -caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthalic acid or pivalolactone and mixtures thereof.
  • Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the structural component for the polyester polyols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • the corresponding chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones can also be used.
  • the multifunctional, polymerizable compound can be urethane (meth) acrylates, epoxy (meth) acrylates or carbonate (meth) acrylates.
  • Urethane (meth) acrylates can be obtained, for example, by reacting polyisocyanates with hydroxyalkyl (meth) acrylates or vinyl ethers and, if appropriate, chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols.
  • Urethane (meth) acrylates which are dispersible in water without the addition of emulsifiers additionally contain ionic and / or nonionic hydrophilic groups which are introduced into the urethane, for example, by structural components such as hydroxycarboxylic acids.
  • the usable polyurethanes essentially contain as structural components:
  • Component (a) includes, for example, aliphatic, aromatic and cycloaliphatic di- and polyisocyanates with an NGO functionality of at least 1.8, preferably 1.8 to 5 and particularly preferably 2 to 4, and their isocyanurates, biurets , Allophanate and Uretdione.
  • the diisocyanates are preferably isocyanates with 4 to 20 carbon atoms.
  • Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, and tysethyl diisocyanate, 4-, 1,3- or 1,2-diisocyanate cyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis (isocyanatomethyl) cycl ⁇
  • Mixtures of the diisocyanates mentioned can also be present.
  • Hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane are preferred.
  • Polyisocyanates which contain isocyanurate groups are polyisocyanates, uretdione diisocyanates, biuret group-containing polyisocyanates, urethane or allophane polyisocyanates containing nate groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates of linear or branched C -C 2 o -alkylene diisocyanates, cycloaliphatic diisocyanates with a total of 6 to 20 C atoms or aromatic diisocyanates with a total of 8 to 20 C atoms or mixtures thereof ,
  • Aliphatic or cycloaliphatic di- and polyisocyanates e.g. the aliphatic or cycloaliphatic diisocyanates mentioned above, or mixtures thereof.
  • Isocyanurate group-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates Particular preference is given to the corresponding aliphatic and / or cycloaliphatic isocyanato-to-isocyanurates and in particular those based on hexamethylhyisocyanate and isophorone diisocyanate.
  • the isocyanurates present here are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologues which have more than one isocyanurate ring.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO functionality of 3 to 4.5.
  • Uretdione diisocyanates with aromatic, aliphatic and / or cycloaliphatic isocyanate groups, preferably aliphatic and / or cycloaliphatic bound and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the uretdione diisocyanates can be used in the preparations as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).
  • These polyisocyanates containing biuret groups generally have an NCO content of 18 to 22% by weight and an average NCO functionality of 3 to 4.5.
  • These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NGO functionality of 2.5 to 3.
  • Polyisocyanates containing oxadiazinetrione groups preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Such polyisocyanates containing oxadiazinetrione groups can be prepared from diisocyanate and carbon dioxide.
  • the polyisocyanates 1) to 6) can be used in a mixture, if appropriate also in a mixture with diisocyanates.
  • Compounds (b) which have at least one group which is reactive toward isocyanate and at least one radical-polymerizable group are suitable as component (b).
  • Groups reactive toward isocyanate can be, for example, -OH, -SH, -NH 2 and -NHR 3 , where R 3 is hydrogen or an alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, / so-propyl, n -Butyl, / so-butyl, se c-butyl or tert-butyl.
  • Components (b) can be, for example, monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid or vinyl ethers with di- or polyols, which are preferably 2 to 20 carbon atoms and have at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 1-dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1 , 4-butanediol, 1,5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 2-methyl-1, 5-pentanedi
  • esters or amides of (meth) acrylic acid with amino alcohols for. B. 2-aminoethanol, 2- (methylamino) ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-aminoethoxy) ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine, or Vinylacetic acid can be used.
  • Unsaturated polyether or polyesterols or polyacrylate polyols with an average OH functionality of 2 to 10 are also suitable.
  • amides of ethylenically unsaturated carboxylic acids with amino alcohols are hydroxyalkyl (meth) acrylamides such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethyl methacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide, N-hydroxyalkylcrotonotone such as N-hydroxymethyl amide or N-hydroxyalkyl maleimides such as N-hydroxyethyl maleimide.
  • hydroxyalkyl (meth) acrylamides such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethyl methacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide, N-hydroxyalkylcrotonotone such as N-hydroxymethyl amide or N-hydroxyalkyl maleimides such as N-hydroxyethyl maleimide.
  • 2-Hydroxyethyl (meth) acrylate, 2- or 3-hydroxypfopyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1 are preferably used , 6-hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate as well as 4-hydroxybutyl vinyl ether, 2-aminoethyl (meth ) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-aminobutyl (meth) acrylate, 6-amino
  • Component (c) is a compound which contains at least two groups which are reactive toward isocyanate, for example -OH, -SH, -NH 2 or -NHR 4 , in which R 4 is, independently of one another, hydrogen, methyl, ethyl, / so- Propyl, n-propyl, n-butyl, / so-butyl, se / -butyl or fatty butyl may have.
  • diols or polyols such as hydrocarbon diols having 2 to 20 carbon atoms, for example ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,1-dimethylethane-1,2-diol, 1,6-hexanediol, 1,10-decanediol, bis- (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctane diol, norbornanediol, pinanediol, decalin diol, etc., their esters with short-chain dicarboxylic acids, such as adipic acid, cyclohexanedicarboxylic acid, their carbonates, prepared by reacting the diols with phosgene or by transesterification
  • Diethylene glycol triethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, pentaerythritol, 1,2- and 1,4-butanediol, 1, 5-pentanediol, 2-methyl-1,5-pentanediol, 2-ethyl- 1,4-butanediol, 1,2-, 1,3- and 1,4-dimethylolcyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, dipentaerythritol, ditrimethylolpropane, erythritol and sorbitol, 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-aminoethoxy) ethanol, bisphenol A, or butanetriol.
  • Unsaturated polyether or polyesterols or polyacrylate polyols with an average OH functionality of 2 to 10 are also suitable, as are polyamines, e.g. Polyethyleneimine or free amine group containing polymers of e.g. Poly-N-vinyl formamide.
  • cycloaliphatic diols such as e.g. Bis (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, cyclooctanediol or norbornanediol.
  • the polyurethanes that can be used are obtained by reacting components (a), (b) and (c) with one another.
  • (a) can generally be chosen as desired, preferably as follows:
  • the formation of the adduct from a compound containing isocyanate groups and the compound which contains groups reactive toward isocyanate groups is generally carried out by mixing the components in any order, if appropriate at elevated temperature.
  • the compound which contains groups reactive toward isocyanate groups is preferably added to the compound containing isocyanate groups, preferably in several steps.
  • the compound containing isocyanate groups is particularly preferably introduced and the compounds which contain groups reactive toward isocyanate are added.
  • the isocyanate group-containing compound (a) is introduced and then (b) is added. If desired, further desired components can subsequently be added.
  • reaction is carried out at temperatures between 5 and 100 ° C, preferably between 20 to 90 C C and particularly preferably between 40 and 80 ° C and in particular between 60 and 80 ° C.
  • Anhydrous means that the water content in the reaction system is not more than 5% by weight, preferably not more than 3% by weight and particularly preferably not more than 1% by weight.
  • the reaction can be carried out in the presence of at least one suitable inert gas, e.g. Nitrogen, argon, helium, carbon dioxide or the like, but this is generally not necessary.
  • suitable inert gas e.g. Nitrogen, argon, helium, carbon dioxide or the like, but this is generally not necessary.
  • the reaction can also be carried out in the presence of an inert solvent, e.g. Acetone, / so-butyl methyl ketone, toluene, xylene, butyl acetate or ethoxyethyl acetate.
  • an inert solvent e.g. Acetone, / so-butyl methyl ketone, toluene, xylene, butyl acetate or ethoxyethyl acetate.
  • the urethane (meth) acrylates preferably have a number average molecular weight M n of 500 to 20,000, in particular from 500 to 10,000, particularly preferably 600 to 3000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
  • the urethane (meth) acrylates preferably have a content of 1 to 5, particularly preferably 2 to 4, moles of (meth) acrylic groups per 1000 g of urethane (meth) acrylate.
  • Epoxy (meth) acrylates can be obtained by reacting epoxides with (meth) acrylic acid.
  • suitable epoxides are epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.
  • Epoxidized olefins can be, for example, ethylene oxide, propylene oxide, / so-butylene oxide, 1-butene oxide, 2-butene oxide, vinyloxirane, styrene oxide or epichlorohydrin, preference is given to ethylene oxide, propylene oxide, / so-butylene oxide, vinyloxirane, styrene oxide or epichlorohydrin, particularly preferably ethylene oxide , Propylene oxide or epichlorohydrin and very particularly preferably ethylene oxide and epichlorohydrin.
  • Aromatic glycidyl ethers are e.g. Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol / dicyclopentadiene, e.g. 2,5-bis [(2,3-epoxypropoxy) phenyl] octahydro-4,7-methano-5H-indene) (CAS No. [13446-85-0]), Tris [4- (2,3- epoxypropoxy) phenyl] methane isomers) CAS no. [66072-39-7]), phenol based epoxy novolaks (CAS No. [9003-35-4]) and cresol based epoxy novolaks (CAS No. [37382-79-9]).
  • Bisphenol A diglycidyl ether bisphenol F diglycidyl ether
  • aliphatic glycidyl ethers examples include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,1,2,2-tetrakis [4- (2,3-epoxypropoxy) phenyl] ethane (CAS No. [ 27043-37-4]), diglycidyl ether of polypr ⁇ pyleriglycol ( ⁇ , ⁇ -bis (2,3-epoxypropoxy) poly (oxypropylene) (CAS No. [16096-30-3]) and of hydrogenated bisphenol A (2 , 2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, CAS No. [13410-58-7]).
  • the epoxy (meth) acrylates and vinyl ethers preferably have a number average molecular weight M n of from 200 to 20,000, particularly preferably from 200 to 10,000 g / mol and very particularly preferably from 250 to 3000 g / mol; the content of (meth) acrylic or vinyl ether groups is preferably 1 to 5, particularly preferably 2 to 4 per 1000 g of epoxy (meth) acrylate or vinyl ether epoxide (determined by gel permeation chromatography with polystyrene as the standard and tetrahydrofuran as the eluent).
  • Carbonate (meth) acrylates contain on average preferably 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) acrylic groups and very particularly preferably 2 (meth) acrylic groups.
  • the number average molecular weight M n of the carbonate (meth) acrylates is preferably less than 3000 g / mol, particularly preferably less than 1500 g / mol, particularly preferably less than 800 g / mol (determined by gel permeation chromatography with polystyrene as standard, solvent tetrahydrofuran).
  • the carbonate (meth) acrylates can be obtained in a simple manner by transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, for example hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or transesterification with (meth) acrylic acid esters, as described for example in EP-A 92269. They are also available by reacting phosgene, urea derivatives with polyhydric, for example dihydric alcohols.
  • vinyl ether carbonates can also be obtained by reacting a hydroxyalkyl vinyl ether with carbonic acid esters and, if appropriate, dihydric alcohols.
  • (meth) acrylates or vinyl ethers of polycarbonate polyols such as the reaction product of one of the di- or polyols mentioned and a carbonic acid ester and a hydroxyl-containing (meth) acrylate or vinyl ether.
  • Suitable carbonic acid esters are e.g. Ethylene, 1,2- or 1,3-propylene carbonate, carbonic acid dimethyl, diethyl or dibutyl ester.
  • Suitable hydroxy group-containing (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acylate, neopentyl glycol mono (meth) acrylate, glycerol mono- and di (meth ) acrylate, trimethylol propane mono- and di (meth) acrylate and pentaerythritol mono-, di and tri (meth) acrylate.
  • Suitable hydroxy group-containing vinyl ethers are e.g. 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.
  • Particularly preferred carbonate (meth) acrylates are those of the formula:
  • R is H or CH 3
  • X is a C 2 -C 18 alkylene group and n is an integer from 1 to 5, preferably 1 to 3.
  • R preferably represents H and X preferably represents C 2 -C 10 alkylene, for example 1,2-ethylene, 1, 2-propylene, 1,3-propylene, 1,4-butylene or 1,6-hexylene, particularly preferred for C 4 - to C 8 -alkylene.
  • X very particularly preferably represents C 6 -alkylene.
  • the carbonate (meth) acrylates are preferably aliphatic carbonate (meth) acrylates.
  • urethane (meth) acrylates are particularly preferred.
  • Antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents can be used, for example, as further paint-typical additives.
  • a pigment containing cerium does not act as a significant cerium source in the sense of this invention due to its low solubility which characterizes pigments.
  • the solubility of pigments is usually not more than 1 g / 1000 g of application medium at 25 ° C.
  • accelerators for thermal post-curing e.g. Tin octoate, zinc octoate, dibutyltin laurate or diaza [2.2.2] bicyclooctane can be used.
  • thermally activatable initiators can also be added, e.g. Potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobis / so-butyronitrile, cyclohexylsulfonylacetyl peroxide, di- / so-propyl percarbonate, tett-butyl peroctoate or benzpinacol, and also, for example, the thermally activatable half-life initiators Have 80 ° C of more than 100 hours, such as di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, silylated pinacoles, the z.
  • the thermally activatable half-life initiators Have 80 ° C of more than 100 hours, such as di-t-butyl peroxide, cumene hydroperoxide, di
  • ADDID 600 from Wacker or amine N-oxides containing hydroxyl groups, such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6- Tetramethylpiperidine-N-oxyl etc.
  • chelating agents e.g. Ethylenediamine acetic acid and its salts as well as ⁇ -di-ketones are used.
  • Suitable fillers include silicates, e.g. B. by hydrolysis of silicon tetrachloride available silicates such as Aerosil ® from Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates etc.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin ® brands from Ciba specialty chemistry) and benzophenones. These can be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or their derivatives, e.g. B. bis- (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate. Stabilizers are usually used in amounts of 0.1 to 5.0% by weight, based on the solid components contained in the preparation.
  • composition of the coating compositions is usually as follows:
  • the proportion of the at least one further photoinitiator apart from the cerium compound can be up to 5% by weight, preferably up to 4, particularly preferably up to 3 and very particularly preferably up to 2.5.
  • the proportion of the at least one photoinitiator can be 0% by weight, preferably at least 0.1% by weight, particularly preferably at least 0.2, very particularly preferably at least 0.3 and in particular at least 0.5% by weight.
  • the proportion of the solvent can be up to 25% by weight, up to 20, up to 15 and very particularly preferably up to 12% by weight.
  • the lower limit is determined by the minimum amount required to dissolve the at least one cerium (IV) compound in the coating composition. This can be worked out by simple solubility tests.
  • the amount of solvent is preferably kept as low as possible.
  • the proportion of the at least one compound capable of free radical polymerization can make up the entire rest of the coating composition apart from cerium (IV) compound and any solvent present.
  • the proportion can be up to 99.9% by weight, preferably up to 98, particularly preferably up to 95, very particularly preferably up to 90% by weight and in particular up to 85% by weight.
  • the proportion of at least one radical-polymerizable compound is at least 25% by weight, preferably at least 50, particularly preferably at least; 65 and very particularly preferably at least 75% by weight.
  • paint-typical additives up to 50% by weight, preferably 1 to 50, particularly preferably 5 to 30 and very particularly preferably 20 to 30% by weight of further paint-typical additives can be present.
  • the requirement here is that the sum of all components is 100% by weight.
  • the present invention further provides a method for starting a radical polymerization and a method for curing coating compositions, in which the coating composition to be cured contains at least one cerium (IV) compound and the coating composition is allowed to act on high-energy radiation.
  • polymerization inhibitors are present in the coating composition, these are deactivated in a preferred embodiment of the invention. This can be done, for example, by carrying out curing in the absence of oxygen, for example under an inert gas, in the case of aerobic polymerization inhibitors, that is to say those which require the presence of oxygen to inhibit radical polymerizations. It can also be useful to remove traces of oxygen from the coating mass by flushing the coating mass with an inert gas. In the presence of aerobic polymerization inhibitors in the coating composition, the inhibition can generally be abolished by exposing the coating composition to a radiation dose required to initiate the polymerization and / or by increasing the amount of cerium (IV) compounds.
  • the radical polymerization is carried out in the absence of polymerization inhibitors and co-stabilizers.
  • the coating compositions containing the mixtures according to the invention can be sprayed using a wide variety of spraying methods, such as air pressure, airless or electrostatic spraying, using one- or two-component spraying systems, but also by spraying, filling, knife coating, brushing, rolling, rolling, pouring. ß, laminating, back injection or co-extrusion can be applied.
  • the coatings are generally dried and cured under normal temperature conditions, ie without heating the coating.
  • the mixtures according to the invention can also be used to produce coatings which, after application, are dried and cured at elevated temperature, for example at 40-250 ° C., preferably 40-150 ° C. and in particular at 40 to 100 ° C.
  • the substrates are coated by customary processes known to the person skilled in the art, at least one coating composition according to the invention or a coating formulation containing the latter being applied to the substrate to be coated in the desired thickness and the volatile constituents of the coating compositions being removed, if appropriate with heating. If desired, this process can be repeated one or more times.
  • the application to the substrate can in a known manner, for. B. by spraying, filling, knife coating, brushing, rolling, rolling or pouring.
  • the coating thickness is generally in a range from about 3 to 1000 g / m 2 and preferably 10 to 200 g / m 2 .
  • a method for coating substrates is disclosed in which the coating composition according to the invention or lacquer formulations containing them, optionally mixed with thermally curable resins, is applied to the substrate, dried, and then with electron beams or UV exposure under an oxygen-containing atmosphere or preferably under Inert gas cures, if necessary at temperatures up to the drying temperature.
  • the process for coating substrates can also be carried out in such a way that after application of the coating composition or coating formulations according to the invention, irradiation is carried out first with electron beams or UV exposure under oxygen or preferably under inert gas in order to achieve pre-curing, and then at temperatures up to 160 ° C , preferably between 60 and 160 ° C, thermally treated and then finally hardened with electron beams or UV exposure under oxygen or preferably under inert gas.
  • Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulse lamps, metal halide lamps, electron flash devices, which enables radiation curing without a photoinitiator, or excimer lamps.
  • High-pressure mercury vapor lamps, lasers, pulsed lamps (flashing light), halogen lamps or excimer lamps are used as radiation sources.
  • the radiation dose usually sufficient for crosslinking in UV curing is in the range from 80 to 3000 mJ / cm 2 .
  • radiation sources can also be used for curing, e.g. two to four.
  • the drying and / or thermal treatment can also be carried out in addition to or instead of the thermal treatment by NIR radiation, electromagnetic radiation in the wavelength range from 760 nm to 2.5 ⁇ m, preferably from 900 to 1500 nm, being referred to here as NIR radiation.
  • Irradiation can optionally be carried out with the exclusion of oxygen, ⁇ . B. are carried out under an inert gas atmosphere; Suitable inert gases are preferably nitrogen, noble gases / carbon dioxide, or combustion gases. Irradiation can also be carried out by covering the coating material with transparent media. Transparent media are e.g. B. plastic films, glass or liquids, e.g. B. water. Irradiation in the manner as described in DE-A1 19957 900 is particularly preferred.
  • the coating compositions according to the invention and lacquer formulations containing them are particularly suitable for coating substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics; mineral building materials, such as shaped cement blocks and fiber cement boards, or metals or coated metals, preferably of plastics or metals.
  • the coating compositions of the invention are particularly preferably suitable as or in exterior coatings, that is to say those applications which are exposed to daylight, preferably of buildings or parts of buildings, interior coatings, road markings, coatings on vehicles and aircraft.
  • the coating compositions according to the invention are used as or in automotive clearcoats and topcoats.
  • the coating compositions containing the mixtures according to the invention can be used in particular as primers, fillers, pigmented topcoats and clearcoats in the field of car repair or large vehicle painting.
  • the coating compositions are particularly suitable for applications in which a particularly high Application security, weather resistance, optics, resistance to solvents, chemicals and water are required, such as in car repair and large vehicle painting.
  • Example 3 was repeated without the addition of cerium.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des matières d'enduction contenant au moins un composé Cer(IV), au moins un solvant non aqueux, au moins un monomère radicalairement polymérisable, éventuellement au moins un composé polymérisable multifonctionnel et éventuellement d'autres additifs typiques pour les peintures.
PCT/EP2005/002731 2004-03-17 2005-03-15 Composes cer comme promoteurs de durcissement par rayonnement WO2005087873A2 (fr)

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Application Number Priority Date Filing Date Title
DE200410013397 DE102004013397A1 (de) 2004-03-17 2004-03-17 Cer-Verbindungen als Initiatoren für die Strahlungshärtung
DE102004013397.2 2004-03-17

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011117364A1 (fr) * 2010-03-24 2011-09-29 Basf Coatings Gmbh Procédé de fabrication d'un laquage multicouche colorant et/ou à effet

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3341328A (en) * 1964-12-21 1967-09-12 Gen Aniline & Film Corp Photopolymerization system using ceric salts
GB1102910A (en) * 1964-04-30 1968-02-14 Du Pont Improvements relating to the production of polymers
WO1998003557A1 (fr) * 1996-07-24 1998-01-29 Dymax Corporation Composition de revetement reagissant a un sechage a l'oxygene
US20020183414A1 (en) * 1999-12-07 2002-12-05 Sumitomo Electric Chemical grafting onto a substrate and coating composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1102910A (en) * 1964-04-30 1968-02-14 Du Pont Improvements relating to the production of polymers
US3341328A (en) * 1964-12-21 1967-09-12 Gen Aniline & Film Corp Photopolymerization system using ceric salts
WO1998003557A1 (fr) * 1996-07-24 1998-01-29 Dymax Corporation Composition de revetement reagissant a un sechage a l'oxygene
US20020183414A1 (en) * 1999-12-07 2002-12-05 Sumitomo Electric Chemical grafting onto a substrate and coating composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011117364A1 (fr) * 2010-03-24 2011-09-29 Basf Coatings Gmbh Procédé de fabrication d'un laquage multicouche colorant et/ou à effet

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WO2005087873A3 (fr) 2006-04-13

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